CN108203711A - A kind of method of absorption water enhancing immobilized enzyme catalysis synthesizing ethyl hexanoate using in silicon oxide nano pore road - Google Patents
A kind of method of absorption water enhancing immobilized enzyme catalysis synthesizing ethyl hexanoate using in silicon oxide nano pore road Download PDFInfo
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Abstract
The invention belongs to the preparing technical fields of oxygen-containing organic compound, specifically disclose a kind of method of the absorption water enhancing immobilized enzyme catalysis synthesizing ethyl hexanoate using in silicon oxide nano pore road, include the following steps：(1) prepare silica material：The characteristics of silica material has the nano pore structure of two-dimensional arrangements, and absorption water is contained in nano pore, and nano pore is arranged in high-sequential；(2) immobilised enzymes is prepared；(3) ethyl hexanoate is catalyzed and synthesized：Using anhydrous cyclohexane as solvent, immobilised enzymes is catalyst, adds in acid and ethyl alcohol carries out esterification, reaction temperature is controlled at 32 38 DEG C；The dosage of the immobilised enzymes is 48 55g/L, a concentration of 0.28 0.35mol/L of caproic acid, and the molar ratio of caproic acid and ethyl alcohol is 1:1.8‑2.Compared with the ethyl hexanoate synthetic reaction of free enzymatic, equally all it is not in addition plus under water condition, is significantly improved using the active catalytic of the synthesis of this method catalysis ethyl hexanoate, ethyl hexanoate yield can be obviously improved.
Description
Technical field
The invention belongs to the preparing technical fields of oxygen-containing organic compound, relate generally to a kind of utilization silicon oxide nano pore road
The method of interior absorption water enhancing immobilized enzyme catalysis synthesizing ethyl hexanoate.
Background technology
Ethyl hexanoate is a kind of very important fine chemicals, can serve as organic solvent, for organic synthesis, preparation people
Essence etc. is made, it is widely used.Biological enzyme synthesizing ethyl hexanoate is with reaction condition is mild, activity is high, side reaction is few, environment is friendly
The advantages that good.Enzyme-catalyzed reaction condition is mild, selectivity is good, product property is good, but resolvase has dispersion in organic solvent
Unevenness easily assembles the problems such as agglomerating, not high so as to cause the catalytic efficiency of enzyme, and is difficult to recycle.Utilize free enzymatic caproic acid
Esterification is carried out with ethyl alcohol, resolvase, which easily gathers, agglomerating causes catalytic efficiency not high.Resolvase must be deposited in the reaction system
Relatively good catalytic activity can be just shown in the case of a certain amount of water, in the reaction system for being not added with water, resolvase is urged
The catalytic activity for changing the esterification of caproic acid and ethyl alcohol is very low.
Invention content
The purpose of the present invention is to provide a kind of absorption water using in silicon oxide nano pore road to enhance immobilized enzyme catalysis
The method of synthesizing ethyl hexanoate, compared with the ethyl hexanoate synthetic reaction of free enzymatic, all in the reaction system for being not added with water,
Using the raising with obvious effects of immobilized enzyme catalysis synthesis ethyl hexylate, ethyl hexanoate yield is significantly increased.
In order to achieve the above object, base case of the invention is：A kind of absorption water using in silicon oxide nano pore road
Enhance the method for immobilized enzyme catalysis synthesizing ethyl hexanoate, include the following steps：
(1) prepare silica material：The silica material has the nano pore structure of two-dimensional arrangements, in nano pore
Contain absorption water；The aperture of nano pore is 6.5-8nm, specific surface area 900-100cm2g-1, Kong Rongwei 1.2-1.5cm3g-1；
(2) immobilised enzymes is prepared：Immobilised enzymes is prepared as carrier using the silica material of step (1)；
(3) ethyl hexanoate is catalyzed and synthesized：Using anhydrous cyclohexane as solvent, immobilised enzymes is catalyst, adds in acid and second
Alcohol carries out esterification, and reaction temperature control is at 32-38 DEG C, and mixing speed control is for 95-105r/min；The immobilised enzymes
Dosage for 48-55g/L, a concentration of 0.28-0.35mol/L of caproic acid, the molar ratio of caproic acid and ethyl alcohol is 1:1.6-2.
Silica material in the technical program has the nano pore of two-dimensional arrangements, contains abundant suction in nano pore
Attached water, inventor are found through experiments that these absorption water have enhancing for being catalyzed the fixation of caproic acid, ethyl alcohol progress esterification
Change the effect of the catalytic activity of enzyme.The immobilised enzymes being prepared by the use of the silica material as carrier, in not another external adding water
Reaction system in, esterification, which occurs, for the immobilized enzyme catalysis caproic acid and ethyl alcohol can reach 68% caproic acid conversion ratio.And
Under similarity condition, the caproic acid conversion ratio that esterification is only capable of reaching 8% occurs for free enzymatic caproic acid and ethyl alcohol, well below
The caproic acid conversion ratio of immobilised enzymes under the same conditions.
When esterification occurs to carry out for caproic acid and ethyl alcohol, the condition of rationally control reaction enables immobilised enzymes to play most
Big effectiveness；The dosage of immobilised enzymes is controlled, enables immobilised enzymes fully and more rapidly catalysis caproic acid and ethyl alcohol carries out
Esterification；The dosage of caproic acid and ethyl alcohol is controlled, since the price of caproic acid is far above ethyl alcohol, makes ethyl alcohol excessive, it is ensured that caproic acid energy
Enough reactions completely, there is no residues in the reaction system.Caproic acid is catalyzed using this base case and esterification occurs for ethyl alcohol, oneself
The high conversion rate of acid, the yield of ethyl hexylate is more, and effect is very notable.
Further, the immobilised enzymes is prepared using following steps：A, silica material is put into equipped with enzyme solution
In container, stirring and adsorbing 1.2-1.8h；B, the material that filtration step a is obtained, respectively obtains filtrate containing enzyme and much filtrate；C, with containing
Enzyme filtrate rinses much filtrate 3-4 times, then with 190-240mL wash buffer much filtrate, and immobilization is then obtained by filtration again
Enzyme；D, the immobilised enzymes obtained after filtering with filter paper is blotted, is put into 4 DEG C of refrigerators and preserves.Silica material will not be to enzyme
Structure has an impact the performance so as to change enzyme so can retain the structure of enzyme in itself to greatest extent as carrier using it and urge
Change performance.Immobilised enzymes is prepared using the above method, while enzyme can be immobilized on silica material well, silica material
The particle morphology of material and the two-dimensional arrangements nano pore structure of high-sequential can also be kept well, will not be by broken
It is bad, it is ensured that the absorption water in silica material nano pore can be good at contacting with enzyme, enhance its catalytic activity.
Further, the dosage of the silica material is 0.4-0.65g, and the dosage of enzyme solution is 90-120ml.By multiple
Experiment finds that, using above-mentioned dosage, enzyme can be preferably supported on silica material.
Further, the silica material is prepared using following steps：(1) P123 is added in into HCl solution, is stirred
Obtain clear solution；(2) by obtained clear solution at 32-38 DEG C static balance 1h；(3) TEOS is added in step (2) and obtained
To solution in be stirred, back hydrolysis obtains hydrolysed mix；(4) hydrolysed mix for obtaining step (3) is in 98-
32-38h is handled at 102 DEG C；(5) material of filtration step (4), obtains white solid, the white filtered out with deionized water flushing
Solid；(6) white solid after flushing is dried at room temperature for, then calcination obtains white powder.It is prepared using the above method
Silica material is obtained, obtained silica material has the nano pore structure of two-dimensional arrangements, and nano pore is in high-sequential
The characteristics of arrangement, nano pore is interior containing abundant absorption water, prepares immobilised enzymes by the use of the silica material as carrier, receives
Abundant absorption water effectively enhances the catalytic activity of immobilised enzymes in metre hole road.
Further, the dosage of the P123 is 20-26g；The HCl solution volume is 660-800ml, a concentration of 0.38-
0.42mol/L；The TEOS dosages are 50-60ml.It is obtained by test of many times, silica material is prepared using said ratio,
Obtained silica material performance is more superior.
Further, in the step of preparing silica material (3), the temperature of reflux is 33-38 DEG C, and the time of reflux is 20-
28h.By state modulator in above range, be conducive to obtain hydrolysed mix.
Further, in the step of preparing silica material (6), the temperature of calcination is 540-560 DEG C, time 3.8-
4.2h.Surfactant is also stained on the silica material obtained by step (5), to obtain more pure silica material
Material need to remove surfactant, and the excessively high sintering that can lead to material of calcination temperature, obtained by test of many times, parameter is set
Range above is set to, surfactant can be preferably removed on the basis of silica material is not destroyed.
Further, the enzyme solution is prepared using following steps：Lipase is taken to do during enzyme powder is added in buffer solution, is stirred
0.8-1.2h is mixed, static 1.5-2h takes supernatant；The lipase does the dosage of enzyme powder as 4.8-5.2g, the dosage of buffer solution
For 1L.Lipase is selected to prepare enzyme solution, lipase helps to catalyze and synthesize ethyl hexanoate, in simultaneous oxidation silicon materials nano pore
Absorption water have the function of to enhance catalytic activity of lipase, help to improve the synthetic quantity of ethyl hexanoate.
Further, the buffer solution is phosphoric acid-citrate buffer solution of pH value 4.01-4.08.When preparing immobilised enzymes, choosing
With phosphoric acid-citrate buffer solution of the pH value, the unstable lipase of silica support adsorption can be effectively removed；It prepares
During enzyme solution, phosphoric acid-citrate buffer solution of the pH value is selected, enzyme solution better performances are prepared.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph (a, b) of silica material and transmission electron microscope picture (c, d) that the present invention uses；
Fig. 2 is the Mass Spectrometer Method figure of absorption water detachment assays that the silica material that the present invention uses carries out；
Fig. 3 be the present invention use silica material load immobilized enzyme catalysis agent scanning electron microscope (SEM) photograph (a, b) and
Transmission electron microscope picture (c, d)；
Fig. 4 is the UV-Vis DRS figure of resolvase, the silica material that the present invention uses, immobilised enzymes；
Fig. 5 is the catalytic activity of the esterification of the caproic acid that resolvase and immobilised enzymes are catalyzed under the same conditions and ethyl alcohol
Comparison diagram.
Specific embodiment
Raw material selection is illustrated below, and is described in detail by taking embodiment 1 as an example and a kind of to utilize silicon oxide nano pore
The method of absorption water enhancing immobilized enzyme catalysis synthesizing ethyl hexanoate in road, other embodiments embody in table 1, unshowned
Part is same as Example 1.
It prepares the lipase that immobilised enzymes is used and does enzyme powder and come from Shenzhen Lv Weikang bioengineering Co., Ltd, according to state
It is 100000U/g to mark the enzyme activity that (GB/T 23535-2009) inner olive oil emulsion process measures；The resolvase used in comparative example
It is all to come from the lipase of Shenzhen Lv Weikang bioengineering Co., Ltd to do enzyme powder, enzyme activity 100000U/g.In immobilised enzymes
Enzyme powder is done comprising silica material and lipase, about enzyme powder is done containing 5g lipase in the immobilised enzymes of 50g.
The P123 that the present invention uses is a kind of triblock copolymer, and full name is:Polyethylene oxide-polypropylene oxide-polycyclic
Oxidative ethane triblock copolymer is a kind of nonionic surfactant, from Aldrich.
Caproic acid that the present invention uses, ethyl alcohol, anhydrous cyclohexane, TEOS are all analytical reagents, from Aldrich.
The buffer solution that the present invention uses is phosphoric acid-citrate buffer solution, using analytically pure citric acid, NaH2PO4·2H2O
And Na2HPO4·12H2O preparation of reagents, these reagents come from Chengdu section dragon chemical industry.
Embodiment 1
A kind of method of absorption water enhancing immobilized enzyme catalysis synthesizing ethyl hexanoate using in silicon oxide nano pore road, packet
Include following steps：
(1) prepare silica material：As shown in Figure 1, silica material has the nano pore of two-dimensional arrangements, nano pore
It is interior containing absorption water, nano pore in high-sequential arrange the characteristics of；The aperture of nano pore is 7.5nm, and specific surface area is
950cm2g-1, Kong Rongwei 1.3cm3g-1.Silica material is prepared using following steps：A, to a concentration of 0.4mol/L, body
P123 of the product to add in 23g in the HCl solution of 700ml, stirs to obtain clear solution.B, obtained clear solution is put down at 35 DEG C
Weigh 1h.C, it will add in the solution obtained to step b and be stirred for 55ml TEOS, back hydrolysis, the temperature of reflux is 35
DEG C, the time of reflux is for 24 hours, obtains hydrolysed mix.D, the hydrolysed mix that step c is obtained is handled into 36h at 100 DEG C.
E, filtration step d materials, obtain white solid, the white solid filtered out with deionized water flushing.F, the white after flushing is consolidated
Body is dried at room temperature for, and then calcination obtains white powder in Muffle furnace, and the temperature of calcination is 550 DEG C, time 4h.
(2) immobilised enzymes is prepared：Include the following steps：A, silica material is put into the container equipped with enzyme solution, stirred
1.5h is adsorbed, the wherein dosage of silica material is 0.5g, and the dosage of enzyme solution is 100ml.Enzyme solution is prepared into using following steps
It arrives：Lipase is taken to do enzyme powder to be added in the buffer solution that pH value is 4.06,1h, static 1.5h is stirred, takes supernatant, supernatant is
For enzyme solution；The dosage that wherein lipase does enzyme powder is 5g, and the dosage of buffer solution is 1L.B, the material that filtration step A is obtained, respectively
Obtain filtrate containing enzyme and much filtrate.C, with filtrate containing enzyme to much filtrate rinse 4 times, then with 200mLpH values be 4.06 buffer solution
Much filtrate is rinsed, immobilised enzymes is then obtained by filtration again.D, the immobilised enzymes obtained after filtering with filter paper is blotted, is put into 4
DEG C refrigerator in preserve.
(3) ethyl hexanoate is catalyzed and synthesized：Using anhydrous cyclohexane as solvent, immobilised enzymes is catalyst, adds in acid and second
Alcohol carries out esterification, and reaction temperature control is at 35 DEG C, and mixing speed control is for 100r/min；The wherein dosage of immobilised enzymes
For 50g/L, a concentration of 0.3mol/L of caproic acid, the molar ratio of caproic acid and ethyl alcohol is 1:1.8.
Table 1
Comparative example 1
Comparative example 1 and embodiment 1 difference lies in：There is no the operation of step (1), (2), step (3) caproic acid and ethyl alcohol hair
Raw esterification：Using anhydrous cyclohexane as solvent, resolvase is catalyst, adds in acid and ethyl alcohol carries out esterification, reaction
Temperature control is at 35 DEG C, and mixing speed control is for 100r/min；Wherein the dosage of resolvase is 5g/L, and caproic acid is a concentration of
The molar ratio of 0.3mol/L, caproic acid and ethyl alcohol is 1:1.8.
Analytic explanation：
Embodiment 1 and comparative example 1 are compared, it can be seen that the caproic acid conversion ratio in embodiment 1 nearly reaches
70%, and the caproic acid conversion ratio in comparative example 1 is well below 20%, as shown in Figure 5.This explanation is being all the reaction that is not added with water
In system, using the effect of the technical program synthesizing ethyl hexanoate far superior to using free Enzyme catalyzed synthesis ethyl hexanoate.
Electron-microscope scanning is carried out to the silica material in embodiment 1, obtains Fig. 1, this material is can see from Fig. 1 a
Particle morphology is uniform, and strip is all presented, and length reaches 20 microns of scale.The higher scanning electricity of resolution ratio shown in Fig. 1 b
The particle in strip that can be recognized in mirror figure in Fig. 1 a is made of the nano pore that sequential 2 D arranges.From Fig. 1 c institutes
In the transmission electron microscope picture shown the it can be seen that end face of the strip particle of this material, by the two-dimensional arrangements subset of cell channels of high-sequential
Into.Fig. 1 d show the side view of the strip particle of this material, and what can be perfectly clear tells height sequential 2 D row
The nano pore of row.The aperture of the silica material of gained is 7.5nm, specific surface area 950cm2g-1, Kong Rongwei 1.3cm3g-1。
Fig. 2 is the Mass Spectrometer Method figure of absorption water detachment assays carried out to the silica material in embodiment 1.It can in figure
See, corresponding H2The signal that the mass number of O is 18 start when desorption temperature is 30 DEG C it is apparent increase, with desorption temperature by
It is cumulative plus and steeply rise, desorption temperature be at 80 DEG C when reach maximum value, be then gradually reduced, at 140 DEG C or so
It is reduced to and the comparable level of baseline.Continuing increases desorption temperature is extremely also not observed other H at 330 DEG C or so2The letter of O
Number.Absorption water detachment assays illustrate that there are abundant absorption water, these absorption water in the nano pore of this silica material to exist
Desorption temperature can be desorbed for 30 DEG C, and it is physical absorption water to illustrate it, have property as the water phase with free state.
The scanning electron microscope (SEM) photograph (a, b) and transmission electron microscope for the immobilised enzymes that Fig. 3 loads the silica material in embodiment 1
Scheme (c, d).The scanning electron microscope (SEM) photograph and transmission electron microscope picture of silica material shown in FIG. 1 are compared, it can be found that by immobilised enzymes
Preparation process, the particle morphology of silica material and the two-dimensional arrangements nano pore structure of high-sequential are obtained for well
It keeps.
Fig. 4 is the UV-Vis DRS figure of resolvase (lipase does enzyme powder), silica material, immobilised enzymes.It can be with
See that the spectrogram of silica material does not all show absorption peak in entire wave-length coverage.The spectrogram of resolvase is then in wavelength
There are one apparent absorption peaks at 276nm；A very strong ABSORPTION EDGE is showed close at 200nm in wavelength.Immobilised enzymes
Spectrogram shows the feature very consistent with the spectrogram of resolvase, equally at 276nm tool there are one apparent absorption peak and
Close to the very strong ABSORPTION EDGE at 200nm.This preparation of explanation by step (1), step (2) in embodiment 1, resolvase by into
It is immobilized on silica material to work(and has obtained immobilised enzymes.
Claims (9)
1. a kind of method of absorption water enhancing immobilized enzyme catalysis synthesizing ethyl hexanoate using in silicon oxide nano pore road, special
Sign is：Include the following steps：
(1) prepare silica material：The silica material has the nano pore structure of two-dimensional arrangements, contains in nano pore
Adsorb water；The aperture of nano pore is 6.5-8nm, specific surface area 900-100cm2g-1, Kong Rongwei 1.2-1.5cm3g-1；
(2) immobilised enzymes is prepared：Immobilised enzymes is prepared as carrier using the silica material of step (1)；
(3) ethyl hexanoate is catalyzed and synthesized：Using anhydrous cyclohexane as solvent, immobilised enzymes is catalyst, add in acid and ethyl alcohol into
Row esterification, reaction temperature control is at 32-38 DEG C, and mixing speed control is for 95-105r/min；The use of the immobilised enzymes
It measures as 48-55g/L, a concentration of 0.28-0.35mol/L of caproic acid, the molar ratio of caproic acid and ethyl alcohol is 1:1.6-2.
2. a kind of absorption water enhancing immobilized enzyme catalysis using in silicon oxide nano pore road according to claim 1 synthesizes
The method of ethyl hexanoate, it is characterised in that：The immobilised enzymes is prepared using following steps：
A, silica material is put into the container equipped with enzyme solution, stirring and adsorbing 1.2-1.8h；
B, the material that filtration step a is obtained, respectively obtains filtrate containing enzyme and much filtrate；
C, much filtrate is rinsed 3-4 times, then with 190-240mL wash buffer much filtrate with filtrate containing enzyme, then filtered again
Obtain immobilised enzymes；
D, the immobilised enzymes obtained after filtering with filter paper is blotted, is put into 4 DEG C of refrigerators and preserves.
3. a kind of absorption water enhancing immobilized enzyme catalysis using in silicon oxide nano pore road according to claim 2 synthesizes
The method of ethyl hexanoate, it is characterised in that：The dosage of the silica material is 0.4-0.65g, and the dosage of enzyme solution is 90-
120ml。
4. immobilised enzymes is enhanced according to a kind of absorption water using in silicon oxide nano pore road of claim 1-3 any one of them
The method for catalyzing and synthesizing ethyl hexanoate, it is characterised in that：The silica material is prepared using following steps：
(1) P123 is added in into HCl solution, stirs to obtain clear solution；
(2) by obtained clear solution at 32-38 DEG C static balance 1h；
(3) TEOS is added in the solution obtained to step (2) and be stirred, back hydrolysis obtains hydrolysed mix；
(4) hydrolysed mix for obtaining step (3) handles 32-38h at 98-102 DEG C；
(5) material of filtration step (4), obtains white solid, the white solid filtered out with deionized water flushing；
(6) white solid after flushing is dried at room temperature for, then calcination obtains white powder.
5. a kind of absorption water enhancing immobilized enzyme catalysis using in silicon oxide nano pore road according to claim 4 synthesizes
The method of ethyl hexanoate, it is characterised in that：The dosage of the P123 is 20-26g；The HCl solution volume is 660-800ml,
A concentration of 0.38-0.42mol/L；The TEOS dosages are 50-60ml.
6. a kind of absorption water enhancing immobilized enzyme catalysis using in silicon oxide nano pore road according to claim 4 synthesizes
The method of ethyl hexanoate, it is characterised in that：In the step of preparing silica material (3), the temperature of reflux is 33-38 DEG C, reflux
Time be 20-28h.
7. a kind of absorption water enhancing immobilized enzyme catalysis using in silicon oxide nano pore road according to claim 4 synthesizes
The method of ethyl hexanoate, it is characterised in that：In the step of preparing silica material (6), the temperature of calcination is 540-560 DEG C, when
Between be 3.8-4.2h.
8. a kind of absorption water enhancing immobilized enzyme catalysis using in silicon oxide nano pore road according to claim 2 synthesizes
The method of ethyl hexanoate, it is characterised in that：The enzyme solution is prepared using following steps：Take lipase do enzyme powder be added to it is slow
In in fliud flushing, 0.8-1.2h is stirred, static 1.5-2h takes supernatant；The dosage that the lipase does enzyme powder is 4.8-5.2g, is delayed
The dosage of fliud flushing is 1L.
9. a kind of absorption water enhancing immobilized enzyme catalysis using in silicon oxide nano pore road according to claim 8 synthesizes
The method of ethyl hexanoate, it is characterised in that：The buffer solution is phosphoric acid-citrate buffer solution of pH value 4.02-4.08.
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| CN110438114A (en) * | 2019-07-27 | 2019-11-12 | 华南理工大学 | A kind of nano-cellulose/light-cured resin prepares the method and immobilised enzymes obtained and application of immobilised enzymes |
| CN110438114B (en) * | 2019-07-27 | 2023-02-14 | 华南理工大学 | Method for preparing immobilized enzyme from nano-cellulose/photocuring resin, prepared immobilized enzyme and application |
| CN112028079A (en) * | 2020-08-31 | 2020-12-04 | 山西大学 | Enzyme-loaded silicon oxide millimeter ball and preparation method and application thereof |
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